New liquid phosphoric esters and processes of making same



AUGUST LEOIPOLD LASKA, 0E OFFENBACH-ON-THE-MAIN, AND HANS HEINRICH CHRISTIAN PRILLWITZ, OF FRANKFORT-ON-THE-MAIN, GERMANY, ASSIGNORS TO THE CORPORATION OF GHEMISGHE FABRIK GRIESHEIM-ELEKTRON, OF FRANKFORT-ON-THE-MAIN, GERMANY.

NEW LIQUID rnosrnonrc ESTERS AND rnocnssns or MAKING saris.

No Drawing.

Oifenbach-on-the-Main, Wilhelmsplatz 18,

and Frankfort on the-Main, Danneckerstrasse 35,1espectively, have invented certain new and useful Improvements in New Liquid Phosphoric Esters and' Processes of Making Same; and they do hereby declare the following to be a full, clear, and exact description of the invention such as will enable others skilled in the art to which it appers tains to make and use the'same.

Our invention relates to new liquid phos- .phoric esters of the general formula:

R, R and R meaning radicles of the benzene series, of which at least two are different, and of which at least'one contains an alkyl group in a position, other than para,

and of which in the highest one contains an genated derivatives.

-.- Homogeneous phosphoric esters, containing 3 identical molecular porportions of the same phenol united I with 1 phosphoric radicle, are already known.' Mixed phosphoric esters of the phenols containing various phenols on a phosphoric radicle could not be prepared hitherto and are new products being viscous,- almost colourless oils of little fluorescence, liquid at ordinary temperature, which can be distilled at reduced pressure and are, when sapomfied Application filed April 12,

Specification of Letters IPatent. Patented Atlg. 8, 1922.

1921. Serial no. 460,762.

separated in phosphoric acid and mixtures f f phenols. They are excellently suitable or of plastic artificial bodies.

Our invention is of singular technical value, because the primary compounds for the production of the mixed esters are available in unlimited quantities, the preparation of the hitherto known liquid homogeneous phosphoric esters being possible softening agents for the production only in limited quantities on account of the want of the cresols in question.

The production of the new compounds may be illustrated by the following examples, the parts 'being by weight.

E wample 1. i y 216 parts of meta-cresol are introduced. in

154.- parts of phosphorus oxychloride, .and the mixture is heated at first for some hours temperature until evolution of hydrogen chloride ceases. Then 108 parts of paracresolare added and then again the mixture is heated at a gradually ascending.

temperature, until no vapours of hydrochloric acid escape. On. fractlon'atlng the product of reaction under reduced pressure the ester distills after a little first running,

as an almost colourless degrees- The same result is obtainedfby heating 67, 5 parts of mono-para-cresylic phosoil within a few phoric chloride (prepared, according t0'- Rapp, Annalen-der Chemie, 224, 168) with 71 parts of meta-cresol, until the development of hydrochloric acid is finished. Theproduct of reaction is treated with diluted caustic soda lye, well washed with water,

dried and subjected to afractional d1st1lla- After twicetion under reduced pressure. fractionatin'g almost the whole quantity distills as awater-clear oil with bluish.

216 parts of meta-cresoland 154 parts ofphosphorus oxychloride is prepared, treated with 94 parts of phenol and the mixture 18s gradually heated to 250, until the evolution of hydrogen chloride ceases. By fraca, tional distilling in'vacuo the chief product] is obtained as a light coloured, heavy oil I at 27 9-282 and 21 mm. pressure. Ewampl 1 A mixture of 188 partsof phenoland-1591 parts of phosphorus oxychloride is heated? at first to a moderate, then to a higher temperature, until the evolution of hyrodgetn chloride ceases, and after addition of 108 partsof ortho-cresol it is heated anew, until thereaction is finished. By fractionatingunder reduced pressure thebhief product is separated from lower boiling ingredients and treated with'dilutedcaustic. soda lye for rectification. Fractionated anew the ester distills at290-293 aud 55 -mm. pres- I sure as a light oil of little fluorescence.

' 188 parts of'phenol and. 15 1 parts of phosphorus oxychloride are caused to react at first alone and then with 108 parts of meta-cresol in: the same manner as described in the preceding example. I After working up the product of reaction the ester is obtained as aiviscous oil, clearas water, boilmgat 306-3Q8 and 60 mm. pressure.

Example ,5.

In the same ma'nnenas already shown in several examples, 216 parts of ortho-cresol are worked up with 15 1 parts of phosphorus oxychloride to the intermediate product, which is treated with 108 parts of paracresol. Rectified with diluted caustic soda lye and fractionated the ester distills at 303-305 and 10 mm. pressure as a colour- Example 7. I

. In the same manner the intermediat product is prepared from 216 parts 0 ortho-cresol and 154 parts of phosphorus oxychloride and treated with 108- parts of meta-cresol. In this manner the ester is obtained as an almost colourless heavy oil, boiling at 300-304? at a pressure of 7 0 mm. Now what we claim and desire to secure by Letters Patent is the following:

I R, R and R, meaning-radicles of \ZBIIG series, ofwhich at leasttWo are dif ferent, and of which at leastone contains. an alkyl group in a. position, other than- 1 para, and of which. in the highest one 'con .phoric esters of the general formula letters of "the general forn'1u1a 1. Asia productsthefliquid h sphoric.

the .ben-f. Y

tains an-alkyl group in para'position r'elating to the oxygen-atom, the-liquid 'phos phoric esters being separated, when saponi j tied, into phosphoric acid on the one side and into mixtures of phenols of the benzene series on the other side, being viscous, al- 7 liquid at ordinary temperature, which can be distilled at reduced pressure;

. v o Rz and ltgme'ahing radicles ofthe hen- -zene series, ofwhichat] least two are dif ferent, and offwh-ich at least one contains alkyl" group in a position, other. than para,

and of which in the highest one contains an alkyl groupin p'ara position relating to the ,oxygen-atom, which [consists in treating-a" chloride ofjan arylphosphoricacid with aphenol-of the benzene series in proportions corresponding to the formula above mentioned.

3. As new productsthe liquid phosphoric esters of the general formula 1 on I r0 -oR en R, R, andIi meaning radicles of the benzene series, of which at least two aredifferent, and of which at least one contains a methyl group in a position, other than para, and of which in the highest one con-- tains a methyl group in para position relating to the oxygen-atom, the liquid phosphoric esters being separated, when saponifled, into phosphoric acid on the one side and into mixtures of phenols of the benzene series on the other side, being viscous, almost colourless oils of little fluorescence, liquid at ordinary temperature, which can be distilled at reduced pressure.

4:. A process of making the liquid phos on roon, on,

R, R and R, meaning radicles of the benzene series, of which at least two are difmost colourless oils. of little fluorescence,

ferent, and of which at least one contains i l a methyl group in a positio other than 2. A; process of making the liquid Ph0$- 51" phoric esters of the general formula I I para, and of which in the highest one con tains a methyl group in para position relating to the oxygen-atom, which consists in treating a chloride of an arylphosphoric acid with a phenol of the benzene series in proportions corresponding to the formula above mentioned.

5. As new products the liquid esters of the general formula PO OR! OR2 I R, R, and R meaning radicles of the henzene series, of which at least two are dlfphosphoric ferent and of which-two contain a methylgroup in a position, other than para, relating to the oxygen-atom, the liquid phosphoric esters being separated, when saponified, into phosphoric acid on the one'side and into mixtures of phenols of the benzene series on the other side, being viscous, al-- most colourless oils of little fluorescence, liquid at ordinary temperature, which can be distilled at reduced pressure.

6. A process of making-the liquid phosphoric esters of the general formula PO OR R, R, and R meaning radicles of the benzene series, of which at least two are different and of which two contain a methyl- 'group in a position, other than para, relating to the ox gen-atom, which consists in treating a ch-oride of an arylphosphoric acid with a phenol of the benzene series in pr'oportions'corresponding to the formula above mentioned.

7. As new products the liquid phosphoric esters of the general formula R, R and R, meaning radicles of the ben zene series containing a methyl group in a .position, other than para, relating to the oxygen-atom, of which at least two are dif ferent, the liquid phosphoric esters being separated, when saponified,'into phosphoric acid on the one side and into mixtures of cresols on the other side, being visoous, al-

most colourless oils of a little fluorescence, liquid at ordinary'temperature, which can be distilled at reduced pressure.

8. A process of making-the liquid phosphoric esters of the general formula on POORi 7 OR! B, R, and R meaning radicles of the benzene series, containing a methyl group in a position, other than para, relating to the AUGUST LEOPOLD LAsiiA. ems summer; csmsmr mnwnz. 

